TWI629335B - Semiconductor adhesive - Google Patents

Semiconductor adhesive Download PDF

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TWI629335B
TWI629335B TW103128761A TW103128761A TWI629335B TW I629335 B TWI629335 B TW I629335B TW 103128761 A TW103128761 A TW 103128761A TW 103128761 A TW103128761 A TW 103128761A TW I629335 B TWI629335 B TW I629335B
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semiconductor
adhesive
semiconductor wafer
resin
electrode
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TW103128761A
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TW201510170A (zh
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永田麻衣
竹田幸平
岡山久敏
畠井宗宏
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積水化學工業股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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Abstract

本發明之目的在於提供一種可抑制空隙之半導體用接著劑。本發明係一種半導體用接著劑,用於具有下述步驟之半導體裝置之製造方法者:步驟1,將半導體晶片經由半導體用接著劑而定位於基板上,該半導體晶片於周緣部及較該周緣部更內側之半導體晶片面內形成有突起電極,該突起電極具有由焊料構成之前端部;步驟2,將上述半導體晶片加熱至焊料熔融點以上之溫度使上述半導體晶片之突起電極與上述基板之電極部熔融接合,並使上述半導體用接著劑暫時接著;步驟3,於加壓環境下加熱上述半導體用接著劑而去除空隙;且上述半導體用接著劑於80~200℃之最低熔融黏度為1000Pa‧s以下,藉由小澤法求出於260℃達到反應率40%所需之時間為8秒以上。

Description

半導體用接著劑
本發明係關於一種可抑制空隙之半導體用接著劑。
伴隨半導體裝置之小型化及高密度化,作為將半導體晶片安裝於基板之方法,使用於表面形成有多個突起電極之半導體晶片倒裝晶片安裝受到注目,並迅速擴大。
於倒裝晶片安裝中,作為用以確保接合部分之連接可靠性的方法,可採用如下通常之方法:將半導體晶片之突起電極與基板之電極部接合後,於半導體晶片與基板之間隙注入液狀密封接著劑(底膠)並使其硬化。然而,使用底膠之倒裝晶片安裝存在底膠填充花費時間等問題或縮小電極間之距離及半導體晶片與基板之距離上有極限等問題。
因此,近年來,提出有於基板上塗佈糊狀接著劑後搭載半導體晶片之方法、於半導體晶圓或半導體晶片上供給膜狀或糊狀接著劑後,將附有接著劑之半導體晶片搭載於基板上之方法等所謂先塗佈型倒裝晶片安裝。尤其是於將附有接著劑之半導體晶片搭載於基板上之情形時,可於半導體晶圓上一次供給接著劑,並藉由切割而一次生產大量附有接著劑之半導體晶片,因此期待製程大幅縮短。
然而,先塗佈型倒裝晶片安裝存在如下情況:於使半導體晶片之突起電極與基板之電極部接觸時,在半導體晶片或基板與接著劑之間夾帶空氣而產生空隙,或於將半導體晶片搭載於基板上時之熱壓接步驟中因來自接著劑之揮發成分而產生空隙。此種空隙會導致電極間之短路或成為接著劑中產生裂痕之主要因素。
因此,為了抑制空隙,提出有藉由在加壓環境下進行接著劑之熱硬化反應而使空隙收縮的方法、使用接著劑將半導體晶片與基板暫時接合後,藉由在加壓環境下對暫時接合體進行加熱而使空隙縮小的方法等(例如專利文獻1~2)。然而,即便為該等方法,尤其是於將附有接著劑之半導體晶片搭載於基板上之情形時,容易因基板之凹凸而夾帶空氣,因此未能利用先前之接著劑充分地抑制空隙。
專利文獻1:日本特開2004-311709號公報
專利文獻2:日本特開2009-004462號公報
且說,市場上使用之半導體晶片中有不僅在周緣部且在較周緣部更內側之半導體晶片面內亦具有突起電極的半導體晶片。然而,於使用此種在周緣部及較該周緣部更內側之半導體晶片面內兩者均具有突起電極之半導體晶片的情形時,較周緣部更內側之半導體晶片面內之突起電極會對樹脂流動及加壓效果造成不良影響,因此即便於加壓環境下加熱暫時接合體,先前之接著劑仍未能充分地抑制空隙。
因此,本發明之目的在於提供一種可抑制不僅產生於周緣部 且產生於較周緣部更內側之半導體晶片面內之空隙的半導體用接著劑。本發明係一種半導體用接著劑,其係用於具有下述步驟之半導體裝置之製造方法者:步驟1,將半導體晶片經由半導體用接著劑定位於基板上,該半導體晶片於周緣部及較該周緣部更內側之半導體晶片面內形成有突起電極,該突起電極具有由焊料構成之前端部;步驟2,將該半導體晶片加熱至焊料熔融點以上之溫度,使該半導體晶片之突起電極與該基板之電極部熔融接合,並使該半導體用接著劑暫時接著;步驟3,於加壓環境下加熱上述半導體用接著劑而去除空隙;且上述半導體用接著劑於80~200℃之最低熔融黏度為1000Pa‧s以下,藉由小澤法所求出之於260℃達到反應率40%所需之時間為8秒以上。
以下,對本發明進行詳細說明。
本發明者對用於下述方法之半導體用接著劑進行了研究:將半導體晶片加熱至焊料熔融點以上之溫度而使半導體晶片之突起電極與基板之電極部接合,其後於加壓環境下加熱半導體用接著劑而去除空隙。結果本發明者發現,即便於加壓環境下進行了加熱,當接合突起電極時於半導體用接著劑之硬化過度進行的情形時,亦無法充分地去除空隙,而必須使用即便經由使突起電極接合時之熱歷程亦可極力抑制硬化之接著劑、即硬化速度(反應速度)相對較慢且最低熔融黏度較低之接著劑作為半導體用接著劑。
再者,本發明者亦思考藉由調整接合突起電極時之條件而抑制半導體用接著劑之硬化,但為了接合突起電極,必須保持焊料熔融點以上之溫度(240~300℃左右),因此於僅藉由調整條件而抑制半導體用接著劑之硬化有 極限。
此處,於熱分析、反應速度分析等領域中,已知有根據藉由試樣之示差掃描熱量測量(DSC測量,Differential scanning calorimetry)所得之資料,求出於固定溫度達到特定反應率之時間,被稱作「小澤(Ozawa)法」之分析方法。
本發明者藉由應用小澤法研究用於半導體裝置之製造方法的半導體用接著劑。結果本發明者實現了最低熔融黏度及藉由小澤法求出之260℃的反應率達到40%所需之時間滿足特定範圍的半導體用接著劑,不僅於用在周緣部具有突起電極之半導體晶片的情形,且於用在周緣部及較該周緣部更內側之面內均具有突起電極之半導體晶片的情形時亦充分去除空隙。
本發明之半導體用接著劑係用於具有下述步驟之半導體裝置之製造方法者:步驟1,將半導體晶片經由半導體用接著劑定位於基板上,該半導體晶片於周緣部及較該周緣部更內側之半導體晶片面內形成有突起電極,該突起電極具有由焊料構成之前端部;步驟2,將該半導體晶片加熱至焊料熔融點以上之溫度,使該半導體晶片之突起電極與該基板之電極部熔融接合,並使該半導體用接著劑暫時接著;步驟3,於加壓環境下加熱該半導體用接著劑而去除空隙。
於使用本發明之半導體用接著劑之半導體裝置之製造方法中,首先,進行步驟1:將半導體晶片經由半導體用接著劑定位於基板上,該半導體晶片於周緣部及較該周緣部更內側之半導體晶片面內形成有突起電極,該突起電極具有由焊料構成之前端部。
於上述進行定位之步驟1中,通常使用倒裝晶片接合機等安裝用裝置, 使相機識別半導體晶片之突起電極、基板之電極部、以及設置於半導體晶片及基板上對準標記之位置,藉此於X、Y方向及旋轉方向(θ方向)上自動地進行定位。
作為上述半導體晶片,例如可列舉由矽、砷化鎵等半導體構成,且於周緣部以及較周緣部更內側之面內存在有具有由焊料構成之前端部的突起電極之半導體晶片。再者,具有由焊料構成之前端部的突起電極只要前端部由焊料構成,則可由焊料構成突起電極之一部分,亦可由焊料構成整個突起電極。
供給上述半導體用接著劑之方法並無特別限定,例如可列舉:將膜狀接著劑貼附於基板上或半導體晶片上之方法;將糊狀接著劑填充至注射器並於注射器前端安裝精密噴嘴,使用分配器裝置將該接著劑噴至基板上之方法等。
又,亦可使用如下方法:預先藉由常壓層壓、真空層壓等將膜狀接著劑貼附於晶圓,或藉由旋轉塗佈法等塗佈或印刷糊狀接著劑而形成塗膜,其後藉由刮刀切割、雷射切割等單片化成半導體晶片。常壓層壓雖存在夾帶空氣之情形,但亦可使用與去除空隙之步驟3相同的加壓烘箱(例如,PCO-083TA(NTT Advanced Technology公司製造))等,於加壓環境下加熱接著劑而去除空隙。
於使用本發明之半導體用接著劑的半導體裝置之製造方法中,繼而進行步驟2:將該半導體晶片加熱至焊料熔融點以上之溫度,使該半導體晶片之突起電極與該基板之電極部熔融接合,並使該半導體用接著劑暫時接著。
又,使上述半導體用接著劑暫時接著之步驟2亦通常使用倒裝晶片接合機等安裝用裝置進行。
焊料熔融點通常為215~235℃左右。上述焊料熔融點以上之溫度的較佳下限為240℃,較佳上限為300℃。若溫度未達240℃,則存在突起電極不會充分熔融而未形成電極接合之情況。若溫度超過300℃,則存在自半導體用接著劑產生揮發成分而使空隙增加之情況。又,存在如下情況:進行半導體用接著劑之硬化,於去除空隙之步驟3中半導體用接著劑之流動性下降而無法充分地去除空隙。
將上述半導體晶片加熱至焊料熔融點以上之溫度的時間(保持時間)之較佳下限為0.1秒,較佳上限為3秒。若保持時間未達0.1秒,則存在突起電極不會充分熔融而未形成電極接合之情況。若保持時間超過3秒,則存在自半導體用接著劑產生揮發成分而使空隙增加之情況。又,存在如下情況:進行半導體用接著劑之硬化,於去除空隙之步驟3中半導體用接著劑之流動性下降而無法充分地去除空隙。
於使上述半導體用接著劑暫時接著之步驟2中,較佳對上述半導體晶片施加壓力。壓力只要為形成電極接合之壓力則並無特別限定,較佳為0.3~3MPa。
於使用本發明之半導體用接著劑的半導體裝置之製造方法中,繼而進行步驟3:於加壓環境下加熱該半導體用接著劑而去除空隙。
所謂加壓環境下,意指高於常壓(大氣壓)之壓力環境下。可認為上述去除空隙之步驟3不僅不使空隙成長,而且可積極地去除空隙,因此於使用本發明之半導體用接著劑的半導體裝置之製造方法中,即便於半導體 用接著劑中夾帶空氣之情形時,亦可去除空隙。
作為於加壓環境下加熱上述半導體用接著劑之方法,例如可列舉使用加壓烘箱(例如,PCO-083TA(NTT Advanced Technology公司製造))之方法等。
上述加壓烘箱之壓力的較佳下限為0.1MPa,較佳上限為10MPa。若壓力未達0.1MPa,則存在無法充分地去除空隙之情況。若壓力超過10MPa,則存在半導體用接著劑本身發生變形,對半導體裝置之可靠性造成不良影響之情況。壓力之更佳下限為0.3MPa,更佳上限為1MPa。
於加壓環境下加熱上述半導體用接著劑時之加熱溫度的較佳下限為60℃,較佳上限為150℃。其中,於加壓環境下加熱上述半導體用接著劑時,可保持在固定溫度及固定壓力下,亦可一面升溫及/或升壓一面階段性地改變溫度及/或壓力。
又,為了更確實地去除空隙,於加壓環境下加熱上述半導體用接著劑時之加熱時間較佳為10分鐘以上。
於使用本發明之半導體用接著劑的半導體裝置之製造方法中,亦可於實施去除空隙之步驟3後進行使半導體用接著劑完全硬化之步驟4。
作為使上述半導體用接著劑完全硬化之方法,例如可列舉:於進行去除空隙之步驟3後,在加壓環境下直接提高溫度而使半導體用接著劑完全硬化之方法,於常壓下加熱半導體用接著劑使其完全硬化之方法等。使上述半導體用接著劑完全硬化時之加熱溫度並無特別限定,較佳為150~200℃左右。
本發明之半導體用接著劑之80~200℃的最低熔融黏度為1000Pa‧s以下,藉由小澤法求出之260℃的反應率達到40%所需之時間為8秒以上。
最低熔融黏度及藉由小澤法所求出之260℃的反應率達到40%所需之時間,滿足上述範圍之半導體用接著劑由於硬化速度(反應速度)相對較慢且反應速度之溫度依存性較小,因此可謂是於使半導體用接著劑暫時接著之步驟2中即便經由使突起電極接合時之熱歷程亦極力抑制硬化,且硬化之不均較少的半導體用接著劑。此種半導體用接著劑不僅於使用在周緣部具有突起電極之半導體晶片的情形,而且於使用在周緣部及較該周緣部更內側之面內均具有突起電極之半導體晶片的情形時亦可充分地去除空隙。
再者,最低熔融黏度為藉由流變計測量所求出者,流變計測量可使用旋轉式流變計裝置(例如,VAR-100(Reologica公司製造))進行,所謂熔融黏度,意指於升溫速度5℃/分鐘、頻率1Hz、應變1%之條件下測得之值。
又,小澤法可使用反應速度分析軟體(例如,SII NanoTechnology公司製造)進行,意指下示之分析方法。
首先,對試樣進行3次以上升溫速度不同之示差掃描熱量測量,對溫度T之倒數與升溫速度B之對數(logB)作圖。根據所得直線之斜率,依據下述式(1)算出活化能△E。繼而,根據活化能△E並依據下述式(2)之恆溫劣化式,算出於260℃保持4秒及於260℃保持6秒之情形時的反應率。依據算出保持4秒之情形時的反應率與算出保持6秒之情形時的反應 率,算出於260℃反應率達到40%之所需時間。示差掃描熱量測量可使用DSC裝置(例如,DSC6220(SII NanoTechnology公司製造))進行。(參照小澤丈夫,熱測量1、2(1974)及T.Ozawa,Bull.Chem.Soc.Japan 38,1881(1965))
式(2)中,τ表示恆溫劣化時間。
本發明之半導體用接著劑的80~200℃之最低熔融黏度為1000Pa‧s以下。若最低熔融黏度超過1000Pa‧s,則於去除空隙之步驟3中半導體用接著劑之流動性下降,即便硬化速度為上述範圍內,亦無法充分地去除空隙。更佳上限為400Pa‧s以下。
本發明之半導體用接著劑的80~200℃之最低熔融黏度的下限並無特別限定,較佳下限為10Pa‧s。若最低熔融黏度未達10Pa‧s,則存在填料(fillet)之溢出過多而污染其他裝置之情況。
本發明之半導體用接著劑藉由小澤法求出之260℃的反應率達到40%所需之時間為8秒以上。若反應率達到40%之時間未達8秒,則即便最低熔融黏度為上述範圍內,亦無法抑制半導體用接著劑之硬化,於去除空隙之步驟3中未能充分地去除空隙。又,若反應率達到40%之時間未達8秒,則較周緣部更內側之面內之突起電極有可能對樹脂流動造成不良影響,於去除空隙之步驟3中殘留有特徵性空隙。
本發明之半導體用接著劑可為膜狀,亦可為糊狀,較佳至少 含有熱硬化性樹脂與熱硬化劑。本發明之半導體用接著劑較佳進而含有硬化促進劑。
由於反應速度亦依存於反應體系之濃度,故可藉由調整例如各成分之含量、尤其是硬化促進劑之添加量而將半導體用接著劑之反應率達到40%之時間調整為上述範圍。具體而言,有硬化促進劑之添加量越多,反應速度越上升,硬化促進劑之添加量越少,反應速度越降低之傾向。然而,適當之硬化促進劑之添加量根據各反應體系而不同,因此,為了將半導體用接著劑之反應率達到40%之時間調整為上述範圍,必須適當調整各成分之含量。
又,半導體用接著劑之最低熔融黏度可藉由調整例如熱硬化性樹脂、熱硬化劑、無機填料等之含量而調整為上述範圍。關於本發明之半導體用接著劑,就容易調整最低熔融黏度為上述範圍而言,較佳含有環氧樹脂、側鏈具有環氧基之丙烯酸系樹脂、熱硬化劑及無機填料。
上述熱硬化性樹脂並無特別限定,例如可列舉藉由加成聚合、聚縮合、聚加成、加成縮合、開環聚合等反應而硬化之化合物。作為上述熱硬化性樹脂,具體而言,例如可列舉:脲樹脂、三聚氰胺樹脂、酚樹脂、間苯二酚樹脂、環氧樹脂、丙烯酸系樹脂、聚酯樹脂、聚醯胺樹脂、聚苯并咪唑樹脂、鄰苯二甲酸二烯丙酯樹脂(diallyl phthalate)、二甲苯樹脂、烷基-苯樹脂、環氧丙烯酸酯樹脂、矽樹脂、胺甲酸乙酯樹脂等。其中,就容易將半導體用接著劑之反應率達到40%之時間調整為上述範圍之方面而言,又,就硬化物之物性等方面而言,較佳為環氧樹脂。
上述環氧樹脂較佳為官能基濃度低即環氧當量高。環氧當量 高之環氧樹脂由於與熱硬化劑之反應機率低且反應性低,因此藉由使用此種環氧樹脂,容易將半導體用接著劑之反應率達到40%之時間調整為上述範圍。上述環氧樹脂之環氧當量更佳為200以上,進而較佳為250以上。
上述環氧樹脂並無特別限定,例如可列舉:雙酚A型、雙酚F型、雙酚AD型、雙酚S型等雙酚型環氧樹脂,酚系酚醛清漆型、甲酚酚醛清漆型等酚醛清漆型環氧樹脂,間苯二酚型環氧樹脂、三苯酚甲烷三縮水甘油醚等芳香族環氧樹脂,萘型環氧樹脂、茀型環氧樹脂、環戊二烯型或二環戊二烯型環氧樹脂、聚醚改質環氧樹脂、NBR改質環氧樹脂、CTBN改質環氧樹脂、及該等之氫化物等。其中,較佳為具有蓬鬆結構之環戊二烯型或二環戊二烯型環氧樹脂。環戊二烯型或二環戊二烯型環氧樹脂之立體阻礙大且反應性低,因此藉由使用此種環氧樹脂,容易將半導體用接著劑之反應率達到40%之時間調整為上述範圍。該等環氧樹脂可單獨使用,亦可併用2種以上。
上述環氧樹脂於常溫下可為液狀之環氧樹脂,也可為固體之環氧樹脂,亦可將該等適當組合而使用。
上述於常溫下為液狀之環氧樹脂中,作為市售品,例如可列舉:EPICLON 840、840-S、850、850-S、EXA-850CRP(以上為DIC公司製造)等雙酚A型環氧樹脂;EPICLON 830、830-S、EXA-830CRP(以上為DIC公司製造)等雙酚F型環氧樹脂;EPICLON HP-4032、HP-4032D(以上為DIC公司製造)等萘型環氧樹脂;EPICLON EXA-7015(DIC公司製造)、EX-252(長瀨化成公司製造)等氫化雙酚A型環氧樹脂;EX-201(長瀨化成公司製造)等間苯二酚型環氧樹脂等。
上述於常溫下為固體之環氧樹脂中,作為市售品,例如可列舉:EPICLON 860、10550、1055(以上為DIC公司製造)等雙酚A型環氧樹脂;EPICLON EXA-1514(DIC公司製造)等雙酚S型環氧樹脂;EPICLON HP-4700、HP-4710、HP-4770(以上為DIC公司製造)等萘型環氧樹脂;EPICLON HP-7200系列(DIC公司製造)等二環戊二烯型環氧樹脂;EPICLON HP-5000、EXA-9900(以上為DIC公司製造)等甲酚酚醛清漆型環氧樹脂等。
上述熱硬化劑並無特別限定,可配合上述熱硬化性樹脂而適當選擇先前公知之熱硬化劑。於使用環氧樹脂作為上述熱硬化性樹脂之情形時,作為上述熱硬化劑,例如可列舉:酸酐系硬化劑、酚系硬化劑、胺系硬化劑、雙氰胺等潛伏性硬化劑,陽離子系觸媒型硬化劑等。該等熱硬化劑可單獨使用,亦可併用2種以上。其中,就硬化物之物性等優異之方面而言,較佳為酸酐系硬化劑。
上述酸酐系硬化劑中,作為市售品,例如可列舉:YH-306、YH-307(以上為三菱化學公司製造,常溫(25℃)下為液狀)、YH-309(三菱化學公司製造之酸酐系硬化劑,常溫(25℃)下為固體)等。
上述熱硬化劑之含量並無特別限定,於使用環氧樹脂作為上述熱硬化性樹脂且使用與環氧基等量反應的熱硬化劑之情形時,上述熱硬化劑之含量相對於半導體用接著劑中所含之環氧基的總量之較佳下限為60當量,較佳上限為110當量。若含量未達60當量,則有無法使半導體用接著劑充分硬化之情況。若含量超過110當量,則有尤其因不會對半導體用接著劑之硬化性有助益,使過量之熱硬化劑揮發,而導致成為空隙之原因的情況。含量之更佳下限為70當量,更佳上限為100當量。
上述硬化促進劑並無特別限定,例如可列舉:咪唑系硬化促進劑、三級胺系硬化促進劑等。其中就容易將半導體用接著劑的反應率達到40%之時間調整為上述範圍之方面而言,又,就容易控制用以調整硬化物的物性等反應體系之方面而言,較佳為咪唑系硬化促進劑。
上述咪唑系硬化促進劑並無特別限定,例如可列舉:FUJICURE 7000(T&K TOKA公司製造,常溫(25℃)下為液狀)、咪唑之1位經氰基乙基保護之1-氰基乙基-2-苯基咪唑、由異三聚氰酸保護鹼性之咪唑系硬化促進劑(商品名「2MA-OK」,四國化成工業公司製造,常溫(25℃)下為固體)、2MZ、2MZ-P、2PZ、2PZ-PW、2P4MZ、C11Z-CNS、2PZ-CNS、2PZCNS-PW、2MZ-A、2MZA-PW、C11Z-A、2E4MZ-A、2MAOK-PW、2PZ-OK、2MZ-OK、2PHZ、2PHZ-PW、2P4MHZ、2P4MHZ-PW、2E4MZ‧BIS、VT、VT-OK、MAVT、MAVT-OK(以上為四國化成工業公司製造)等。該等咪唑系硬化促進劑可單獨使用,亦可併用2種以上。
上述硬化促進劑之含量並無特別限定,相對於熱硬化劑100重量份之較佳下限為1重量份,較佳上限為50重量份,更佳下限為2重量份,更佳上限為30重量份。若含量未達2重量份,則有為了進行半導體用接著劑之熱硬化而必須於高溫下進行長時間加熱之情況。若含量超過50重量份,則有半導體用接著劑之儲存穩定性變得不足,或因過量之硬化促進劑揮發導致成為空隙的原因之情況。
於本發明之半導體用接著劑為膜狀接著劑之情形時,較佳進而含有高分子量化合物。藉由使用上述高分子量化合物,可賦予半導體用接著劑製膜性、可撓性等,並使半導體用接著劑之硬化物具有強韌性,確 保高接合可靠性。
上述高分子量化合物並無特別限定,例如可列舉:脲樹脂、三聚氰胺樹脂、酚系樹脂、間苯二酚樹脂、環氧樹脂、丙烯酸系樹脂、聚酯樹脂、聚醯胺樹脂、聚苯并咪唑樹脂、鄰苯二甲酸二烯丙酯樹脂、二甲苯樹脂、烷基-苯樹脂、環氧丙烯酸酯樹脂、矽樹脂、胺甲酸乙酯樹脂等公知之高分子量化合物。其中,較佳為具有環氧基之高分子量化合物。
藉由添加上述具有環氧基之高分子量化合物,半導體用接著劑之硬化物表現出優異可撓性。即,半導體用接著劑之硬化物兼具來自作為上述熱硬化性樹脂之環氧樹脂的優異機械強度、耐熱性及耐濕性、以及來自上述具有環氧基之高分子量化合物的優異可撓性,因此成為耐冷熱循環性、耐回流焊性、尺寸穩定性等優異者,表現高接合可靠性及高導通可靠性。
上述具有環氧基之高分子量化合物只要為在末端及/或側鏈(側鏈位)具有環氧基之高分子量化合物,則無特別限定,例如可列舉:含環氧基之丙烯酸系橡膠、含環氧基之丁二烯橡膠、雙酚型高分子量環氧樹脂、含環氧基之苯氧基樹脂、含環氧基之丙烯酸系樹脂、含環氧基之胺甲酸乙酯樹脂、含環氧基之聚酯樹脂等。其中,就可獲得含有大量環氧基之高分子化合物且成為硬化物之機械強度及耐熱性更優異者而言,較佳為含環氧基之丙烯酸系樹脂。該等具有環氧基之高分子量化合物可單獨使用,亦可併用2種以上。
於使用上述具有環氧基之高分子量化合物、尤其是含環氧基之丙烯酸系樹脂作為上述高分子量化合物之情形時,上述具有環氧基之高 分子量化合物的重量平均分子量之較佳下限為1萬,較佳上限為100萬。若重量平均分子量未達1萬,則有半導體用接著劑之製膜性變得不充分,或半導體用接著劑之硬化物的可撓性未充分提昇之情況。若重量平均分子量超過100萬,則有如下情況:於定位之步驟1中不易以一定之厚度供給半導體用接著劑,或於去除空隙之步驟3中半導體用接著劑之熔融黏度變得過高而流動性下降,無法充分地去除空隙。
於使用上述具有環氧基之高分子量化合物、尤其是含環氧基之丙烯酸系樹脂作為上述高分子量化合物之情形時,上述具有環氧基之高分子量化合物較佳為低官能基濃度即高環氧當量。高環氧當量之高分子量化合物由於反應性低,因此藉由使用此種高分子量化合物,容易將半導體用接著劑的反應率達到40%之時間調整為上述範圍。上述具有環氧基之高分子量化合物之環氧當量更佳為200以上,進而較佳為250以上。
本發明之半導體用接著劑中上述高分子量化合物之含量並無特別限定,較佳下限為3重量%,較佳上限為30重量%。若含量未達3重量%,則有無法獲得針對熱應變之充分可靠性的情況。若含量超過30重量%,則有半導體用接著劑之耐熱性下降的情況。
本發明之半導體用接著劑較佳進而含有無機填料。
上述無機填料並無特別限定,例如可列舉:二氧化矽、氧化鋁、氮化鋁、氮化硼、氮化矽、碳化矽、氧化鎂、氧化鋅等。其中,就流動性優異之方面而言,較佳為球狀二氧化矽,更佳為經甲基矽烷偶合劑、苯基矽烷偶合劑等進行過表面處理之球狀二氧化矽。藉由使用經表面處理之球狀二氧化矽,可抑制半導體用接著劑之增黏,可於去除空隙之步驟3中極有效 率地去除空隙。
上述無機填料之平均粒徑並無特別限定,就半導體用接著劑之透明性、流動性、接合可靠性等觀點而言,較佳為0.01~1μm左右。
本發明之半導體用接著劑亦可視需要進而含有稀釋劑、觸變賦予劑、溶劑、無機離子交換體、防滲劑、咪唑矽烷偶合劑等接著性賦予劑、密合性賦予劑、橡膠粒子等應力緩和劑等其他添加劑。
製造本發明之半導體用接著劑之方法並無特別限定,於為糊狀接著劑之情形時,例如可舉下述方法:於熱硬化性樹脂及熱硬化劑中視需要摻合特定量之硬化促進劑、高分子量化合物、無機填料及其他添加劑並混合。上述混合之方法並無特別限定,例如可列舉使用勻相分散機、萬能混合機、班伯里混合機、捏合機、珠磨機、均質機等之方法。又,為膜狀接著劑之情形時,例如可舉下述方法:於溶劑中添加特定量之相同材料而製備接著劑溶液,將接著劑溶液塗佈於脫模PET膜上,使接著劑溶液乾燥。為膜狀接著劑之情形時,本發明之半導體用接著劑之厚度並無特別限定,較佳為10~50μm,更佳為10~40μm。
根據本發明,可提供一種不僅使用在周緣部具有突起電極之半導體晶片,而使用在周緣部及較該周緣部更內側之面內均具有突起電極之半導體晶片亦可充分地抑制空隙的半導體用接著劑。
以下列舉實施例更加詳細地說明本發明之態樣,但本發明並不僅限定於該等實施例。
(實施例1~4及比較例1~7)
(1)接著劑之製造
依照表1記載之摻合組成,將下示之材料添加至溶劑(甲基乙基酮)中,使用勻相分散機攪拌混合而製造接著劑溶液。
使用敷貼器將所得之接著劑溶液以乾燥後厚度成為40μm之方式塗佈於脫模PET膜上,使接著劑溶液乾燥而製造膜狀接著劑。至使用前,於形成在脫模PET膜上之接著劑層的表面貼附另一脫模PET膜(保護膜)加以保護。
‧HP-7200HH(二環戊二烯型環氧樹脂,環氧當量280,DIC公司製造)
‧EP-4088S(二環戊二烯型環氧樹脂,環氧當量170,ADEKA公司製造)
‧YH-309(酸酐系硬化劑,三菱化學公司製造)
‧FUJICURE 7000(咪唑系硬化促進劑,T&K TOKA公司製造)
‧2MZA-PW(咪唑系硬化促進劑,四國化成工業公司製造)
‧G-2050M(含縮水甘油基之丙烯酸系樹脂,環氧當量340,日油公司製造)
‧G-0250SP(含縮水甘油基之丙烯酸系樹脂,環氧當量310,日油公司製造)
‧YA050C-SP5(二氧化矽填料,Admatechs公司製造)
‧KBE-402(3-縮水甘油氧基丙基甲基二乙氧基矽烷,信越化學工業公司製造)
(2)最低熔融黏度之測量
使用旋轉式流變計裝置(VAR-100,Reologica公司製造)於升溫速度5℃/分鐘、頻率1Hz、應變1%下對所得之接著劑測量「80℃~200℃下之最低熔融黏度」。
(3)示差掃描熱量之測量
於升溫速度1、2、5、10℃/min之4種條件下對所得之接著劑進行示差掃描熱量測量,並對溫度T之倒數與升溫速度B之對數(logB)作圖。根據所得直線之斜率,依據上述式(1)算出活化能△E。繼而,根據活化能△E並依據上述式(2)之恆溫劣化式,算出於260℃保持4秒及於260℃保持6秒之情形時的反應率。
再者,使用示差掃描熱量計(DSC6220,日立高新技術公司製造)及反應速度分析軟體(SII NanoTechnology公司製造)。基於算出之保持4秒之情形時的反應率與保持6秒之情形時的反應率,算出「於260℃反應率達到40%之所需時間」。
(4)半導體裝置之製造
(4-1)將半導體晶片經由接著劑而定位於基板上之步驟1、及使接著劑暫時接著於基板及半導體晶片之步驟2
準備於周緣部及較該周緣部更內側之半導體晶片面內形成有具有由焊料構成之前端部的突起電極之半導體晶片、以及具有Cu/焊料(Solder)電極之基板。將接著劑之單面的保護膜剝離,使用真空層板機(ATM-812M, Takatori公司製造)於平台溫度60℃、真空度100Pa貼附在半導體晶片上。
繼而,使用倒裝晶片接合機(FC-3000S,東麗工程股份有限公司公司製造),將半導體晶片經由接著劑而定位於基板上(步驟1),於接合平台溫度100℃之條件下以160℃接觸而升溫至290℃,並施加0.96Mpa之荷重2.4秒,而使半導體晶片之突起電極與基板之電極部熔融接合,並且使接著劑暫時接著(步驟2)。
(4-2)去除空隙之步驟3
將所得之暫時接著體投入加壓烘箱(VFS,APT公司製造),藉由以下之加壓、加熱條件於加壓環境下加熱接著劑而去除空隙(步驟3),並且使接著劑完全硬化,獲得半導體裝置。
<加壓、加熱條件>
步驟1:於20分鐘內自30℃固定升溫至100℃,0.8MPa
步驟2:於100℃保持60分鐘,0.8MPa
步驟3:於20分鐘內自100℃固定升溫至180℃,0.8MPa
步驟4:於180℃保持10分鐘,0.8MPa
步驟5:於20分鐘內自180℃降溫至30℃,0.8MPa
<評價>
對實施例及比較例中所得之半導體裝置進行以下評價。將結果示於表1。
有無空隙
使用超音波探查影像裝置(C-SAM D9500,Nippon BARNES公司製造)觀察去除空隙之步驟3前後之半導體裝置,而評價有無空隙。將半導體晶 片之產生空隙部分的面積相對於接著面積未達1%之情形記作良品(○),1%以上之情形記作不良品(×)。再者,是良品抑或不良品之判斷係將n數設為5個而對半導體晶片產生空隙之部分的面積相對於接著面積最小之半導體裝置進行。又,將n數設為5個,求出良品率(x/5)。
根據本發明,可提供一種即便使用不僅在周緣部,而在周緣部及較該周緣部更內側之面內均具有突起電極之半導體晶片,亦可充分地抑制空隙的半導體用接著劑。

Claims (1)

  1. 一種半導體用接著劑,用於具有下述步驟之半導體裝置之製造方法:步驟1:將半導體晶片經由該半導體用接著劑定位於基板上,該半導體晶片於周緣部及較該周緣部更內側之半導體晶片面內形成有突起電極,該突起電極具有由焊料構成之前端部;步驟2:將該半導體晶片加熱至焊料熔融點以上之溫度0.1~3秒,使該半導體晶片之突起電極與該基板之電極部熔融接合,並使該半導體用接著劑暫時接著;步驟3:於加壓環境下加熱該半導體用接著劑而去除空隙,該半導體用接著劑之特徵在於:至少含有環氧樹脂與熱硬化劑與硬化促進劑,該熱硬化劑之含量相對於該環氧樹脂之環氧基的總量,為60~110當量,該硬化促進劑之含量相對於該熱硬化劑100重量份,為1~50重量份,該半導體用接著劑於80~200℃之最低熔融黏度為1000Pa‧s以下,藉由小澤法求出於260℃達到反應率40%所需之時間為8秒以上11.8秒以下。
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